Compounds of the coeranthrene and coerbianthrene series



Patented Oct. 17, 1 939 COMPOUNDS OF THE COERANTHRENE AND COERBIANTHRENESERIES Heinrich Hopff, Ludwigshafen-on-the-Rhine, and Karl Heymann,Mannheim, Germany, assignors to General Aniline Works, Inc., New York,N. Y.,

a corporation of Delaware 1 No Drawing. Application September13,1 935,Se-

rial No. 40,411. In Germany October 5, 1934 4 Claims. (Cl. 260335) Thepresent invention relates to compounds of the coeranthrene andcoerbianthrene series and a process of producing same.

Compounds of the coeranthrene and coerbianpractice but the invention isnot restricted to these examples. The parts are by weight.

Example 1 5 threne series have hitherto been prepared by 5 Parts Of4,14dimBthy100e10X0I101 Which has reduction of the correspondingcoeroxonol or the fo u coeroxenol compounds with hydrogen iodide in H3Othe presence of phosphorus. This method of working is not used inpractice by reason of the expensive use of hydrogen iodide, especiallyas \b the resulting products are obtained in an impure HO form.

We have now found that compounds of the coeranthrene and coerbianthreneseries can be obtained very smoothly in a pure form by treat- 15 ing thecorresponding coeroxonols or coeroxenols with reactive hydrogen. Thistreatment may O CH consist in an action of gaseous hydrogen in the 3presence of catalysts or in an electrolytic reducare Suspended WhileStlrrmg 1n Pa ts Of about tion or in a reduction by nascent hydrogen inan 9 per cent caustlc s da ut 5 pa ts of 20 alkaline medium. The saidprocesses may be car- Z1110 dust and, 1f deslred, 29 Parts Of ethyl riedout at ordinary or increased temperature, as 001101 are then added andthe Whole heated to for example at from 60 to 120 C., if de d boilingfor five hours. The end of the reaction der superatmospheric pressure,becomes evident by the fact that the originally The procedure may be, foexample, t t red colored solution becomes markedly paler. 25 saidinitial materials are treated in the presence The mlXtuTe of excessZ1110 dust and the reductlen of olvents or diluents as for example cyc10product is filtered by suction and the latter 1S0- hexane,tetrahydronaphthalene, decahydronaphlated by extraction with organicsolvents. It is thalene or hexane, with hydrogen in the presence ayellow'brewn eduet hi dissolves in e 30 of hydrogenation catalysts, suchas finely divided eentreted Sulphur-Le e glvmg a red coloretlen- 30nickel, copper, cobalt, palladium, or platinum, as A slmilar procedureis followed when employing Such or in admixture t each other or withcoeroxonol instead of dimethylcoeroxonol. Inother substances, as forexample activators, such Stead of Zinc dust alummmm powder may be aszinc, manganese, aluminium, or iron at eleemployed' vated temperature,if desired under superatmos- Example 2 35 pheric pressure. Thecoeroxonols or coeroxenols 5 parts of purified coeroxonol which has themay also be treated in an alkaline medium with formula energeticreducing agents which develop nascent hydrogen, as for example withaluminium, zinc,

tin or lead in the presence of caustic alkaline 40 solutions or ammonia.In many cases it is advantageous to add organic solvents, such as al- HOl cohol or acetone, to the reducing agents which develop nascenthydrogen. Electrolytic reduction 45 in an alkaline medium also yieldsgood results.

The reaction products are obtained in a state of great purity.

The following examples will further illustrate O how the said inventionmay be carried out in are suspended in parts of cyclohexane, 1 part 50of very finely divided nickel powder is added and the whole heated at100 C. with hydrogen under Example 3 5 parts of the dimethylcoeroxenolemployed as starting material in Example 1 are suspended in 100 parts ofan about 20 per cent aqueous caustic soda solution. This suspension isthen subjected to an electrolytic reduction-at 0.02 ampere per squarecentimeter until the initial substance has wholly disappeared. Afterworking up in the usual manner, the reduction product is obtained in theform of a finely divided orange powder which is very readily soluble inorganic solvents especially in benzene giving a beautiful greenfluorescence.

What We claim is:

1. A process of producing compounds of the coeranthrene andcoerbianthrene series which comprises acting on a compound of the classconsisting of coeroxonols and coeroxenols with nascent hydrogen producedin an alkaline medium until compounds practically insoluble in alkaliare obtained.

2. A process of producing compounds of the coeranthrene andcoerbianthrene series which comprises acting on a compound of the classconsisting of coeroxonols and coeroxenols with nascent hydrogen producedby means of a metal in an alkaline medium until compounds practicallyinsoluble in alkali are obtained.

3. A process of producing compounds of the coeranthrene andcoerbianth'rene series which comprises acting on a compound of the class.;consisting of coeroxonols and coeroxenols with 'comprises acting 'on acompound of the class consisting of coeroxonols and coeroxenols toe1ectrolytic reduction with nascent hydrogen produced by electrolysis inan'alkaline medium until compounds practically insoluble in alkali areobtained.

HEINRICH HOPFF. KARL HEYMANN.

